Anti-static coated textile fiber



United States Patent 3,300,337 ANTI-STATIC CUATED TEXTELE FIBER RobertS. Cooper, Park Forest, Ill., assignor t o Stautter Chemical Company,New York, N.Y., a corporation of Delaware I No Drawing. Originalapplication Oct. 6, 1960, Ser. No. 60,788. Divided and this applicationSept. 30, 1963,

Ser. No. 312,326 11 Claims. (Cl. 117- -139,.5)

This application is a division of my copending application, Serial No.60,788, filed October 6, 1960, noW abandoned.

This invention relates to phosphonic. acidswhich have been found to beuseful anti-static agents.

In particular, this invention relates to the .use of 2- carboxyalkylalkylphosphonic acids and their alkali metal and amine salts asanti-static agents.

These compounds may be prepared by reacting a-dialkyl phosphite with anester of an unsaturated mono-, di-, or tricarboxylic acid; hydrolyzingall the ester radicals to. the. freeacidjnd. .then selectivelyre-esterifying .the

s am

in in R R wherein R, R =lower alkyl; R =H, CH COOR R =H, CH CH COOR andR =alkyl.

It is wellkn-own in the art to react dialkyl phosphites with unsaturatedcarboxylic acid esters as illustrated in Equation I. (See A. N. Pudovik,Zhur. Obschei. Khim., 22, 473-7, 1952.) It is also well-known tohydrolyze the resulting ester product to the corresponding acid as inEquation II. Thus, it can be readily seen that the exact alkyl groupswhich are identified by R, and R are immaterial. These radicals are alllost during the hydrolysis. It is the nature of R in the final compound,including its presence in the carboxylic groups of R and R whichdetermines the unusual characteristics of these compounds.

The preferred unsaturated polycarboxylic acids which may be used inpreparing these Compounds include acrylic, methacrylic, erotoni-c,isocrotonic, maleic, fumaric, itaconic, and aconitic acids. Most ofthese acids are readily available commercially and ordinary commercialgrades are satisfactory. As noted above, the particular phosphite usedis unimportant since the ester radicals are converted to acid groups.Therefore, the readily available lower dialkyl phosphites such asmethyl, ethyl, propyl, and butyl, are preferred. The ester groups whichform the basis for these compounds include alkyl radicals containingfrom 1. to 18 carbon atoms. Inpar ticular, I find that the ester groupscontaining from 4 to 12 carbon atoms possess many valuablecharacteristics. I also find thatreactions with dihydroxy alcohols suchas ethylene glycolppropylene glycol, and the like, produce 3,300,337Patented Jan. 24, 1957 w-ot l wherein R and R are as defined above and Ris a lower alkylene radical.

It is also within the scope of my invention to use these compounds inthe form of their alkali metal, ammonium, or amine salts. These saltsmay be made by the conventional means using such representative bases'as sodium and potassium hydroxide, ammonium hydroxide, mono-, -di-, andtrialkyl-amines, mono-, di-, and trialkanolamines, and the like. Inparticular, the lower alkyl, lower alkanol, octyl, lauryl, and stearylamines produce substituted amine salts with valuable properties. As usedherein, the term substituted amino is intended to include the radicalresulting when an amine reacts with an aci-d. Therefore, representativeradicals are diethyl amino [(C H N-], diethanol amino The followingexamples illustrate the compounds useful in my invention Example 1Forty-two grams of (2-c'arboxyli'c acid) propylphosphonic acid (preparedfrom dialkyl phosphate and methyl methacrylate followed by acidhydrolysis), 20.4 grams of n-but-an-Ol and 200 ml. benzene were placedin a flask fitted with a thermometer, water separator and refluxcondenser. The mixture began to reflux at 80 C. and after twenty-threehours, 4.7 moles; of water had been collected (theory, 4.5 The benzeneand excess'butanol were removed by strippingto 100 C. at 1 mm. Hgpressure. The product, a viscous liquid, weighed 52.1 grams (93.0%), andhad an index of refraction N =1.4561. Neutralization equivalents run inalcohol' showed the product to be dibasic. It analyzed 13.4% P, theory13.8%Pf0r I j I I n F (HOMPGHQCHCOOOiHi ExampleZ Ina manner similar toExample 1, 42.0 grants of (Z-carboxylic acid) pro-pylphosphonic acid,32.6 grams of Z-ethyl hexanol and 200 ml. of benzene were placed in thefiask and heated to reflux. After seventy hours of reflux, 4.8 moles ofwater had been collected. Volatiles were removed to C. at 1 mm. leaving64.9 grams (92.6%) of clear, straw colored product having an index ofrefraction N =1.4578. It was-a dibasic acid and analyzed as 11.3% P,theory 11.1% P, for

recovered. Volatiles were removed to C. at l'mm.

to give a viscous liquid analyzing 17.1% P, theory 17.1% P, for

lowing data indicate the reduction in static charge which takes placewhen the fibers are treated with these compounds. All data resulted fromcarefully controlled tests under the same conditions for each comparisonof test sample and untreated blank. The test method briefly involvedweighing a 10 gram wad of the fiber, scouring, drying, desiccating,saturating with a solution of anti-static agent, squeeze drying,weighing to obtain add-on, drying to remove solvent, cooling,conditioning in constant relative humidity (RH) atmosphere,rubbingbriskly to develop charge, and measuring charge by dropping in abrass beaker with grounded voltmeter attached.

Compound A is the diethanolamiue salt of ('l-carboxylmtyl)propylphosphonic acid. Compound B is the diethanolamine salt of(Z-carboxyoctyl) propylphosphonic acid. 1 Concentration of anti-staticagent, and solvent used.

2 Average of 5'tests.

282.8 grams. Analysis showed this product to be about 85% o uonioHornoooon-n;

oooosnn Twenty grams of this product was used to form the sodium salt OI] (NitOhI CIICHgC O c3111.",

0 o 0 can" by neutralizing with NaOH to a pH of 6.5. This product was anexcellent wettingagent as noted in Table II.

Example I The diethanolamine salt of Z-carboxyoctyl propylphosphonicacid was prepared by adding 15.8 grams of diethanolamine gradually to28.1 grams of the phosphonic acid While stirring and cooling the beakerwith ice water. The product was a viscous liquid, neutral to methylorange and soluable in water.

Example 6 i Following the procedure of Example 1, 84.1 grams of(Z-carboxylic acid) propylphosphonic acid, 11.8 grams of lauryl alcohol,and 200 cc. of toluene were placed in the flask and heated to reflux.After twenty-three hours, 12 ml. of water had been removed. Volatileswere then stripped off to 150 C. at 2 mm., yielding 183.1 grams of clearbrown liquid (2-carboxylauryl) propylphosphonic acid. The sodium salt ofthis acid was prepared according to the procedure of Example 4, and thiscompound was found to be an excellent wetting agent, as noted in TableII.

The above compounds have been found to be excellent anti-static (AS)agents on ,various textilefibers. The fol- The Dacron referred to aboveis referred to hereinafter as polyethylene terephthalate. It is thereaction product of dimethylterephthalate and ethylene glycol. (SeeKirk-Othmer, Encyclopedia of Chemical Technology, Interscience 1953,vol. 13, at page 840 et seq.)

The Orlon referred to above is a polyacrylonitrile fiber. (SeeKirk-Othmer, supra, vol. 13 at page 824 et seq.)

The acetate fiber referred to above was a commercial cellulose acetatewhich is representative of a class of similar compounds. These compoundshave been carefully defined by the Federal Trade Commission. (See Kirk-Othmer, supra, vol. 11, at page 550 et seq.)

The above compounds were also tested as wetting agents and found to giveexcellent results. Table II shows the results obtained using thestandard Draves test (Tech. Manual of the Am. Assn. of Textile Chemistsand Colorists 35, 167 (1959) Std. Test Method 171952) to measure thesinking time at various concentrations.

1 Ultrawet K is a synthetic anionic surface active detergent of thehigher alkyl aromatic sulionatc type. It is included for purposes ofcomparison.

The foregoing description has been given for purposes of understandingonly, and no unnecessary limitations should be derived therefrom.

I claim:

1. A static electricity resistant fiber comprising a fiber selected fromthe group consisting of cotton, cellulose acetate, polyethyleneterephthalate, and acrylonitrile polymer having deposited upon thesurface thereof from about 0.5% to about 3% by weight of a compoundselected from the group consisting of (a) a compound of the formula: 5

0 (MO); J( J-C 0 0 R and (b) a compound of the formula:

0 H H [(nIO)2: li COO]2R wherein R is selected from the group consistingof H, CH and COOR R is selected from the group consisting of H, CH andCH COOR R is an alkyl radical containing from 1 to 18 carbon atoms; R isa lower alkyl'ene radical; and M is selected from the group consistingof hydrogen, alkali metal, ammonium, alkyl amine and alkanol amine.

2. A static electricity resistant fiber according to claim 1 wherein thefiber is cotton.

3. A static electricity resistant fiber according to claim 1 wherein thefiber is cellulose acetate.

4. A static electricity resistant fiber according to claim 1 wherein thefiber is polyethylene terephthalate.

5. A static electricity resistant fiber according to claim 1 wherein thefiber is acrylonitrile polymer. 0

6. A static electricity resistant fiber comprising a fiber selected fromthe group consisting of cotton, cellulose acetate, polyethyleneterephthalate, and acrylonitrile polymer having deposited upon thesurface thereof from about 0.5% to about 3% by weight of a compound ofthe formula:

OHH

atom alkyl radical; and M is selected from the group consisting ofhydrogen, alkali metal, ammonium, alkyl amine and alk-anol amine.

7. A static electricity resistant cotton fiber comprising cotton havingdeposited upon the surface thereof, from about 0.5% to about 3% byweight of the diethanolamine salt of (2-carboxybutyl) propylphosphonicacid.

8. A static electricity resistant polyethylene terephthalate fibercomprising polyethylene terephthalate having deposited upon the surfacethereof, from about 0.5% to about 3% by weight of the diethan'eolaminesalt of (2- carboxybutyl) propylphosphonic acid.

9. A static electricity resistant acrylonitrile polymer fiber comprisingacrylonitrile polymer having deposited upon the surface thereof, fromabout 0.5 to about 3% by weight of the diethanolamine salt of(2-carboxybutyl) propylphosphonic acid.

10. A static electricity resistant acetate fiber comprising celluloseacetate having deposited upon the surface thereof, from about 0.5 toabout 3% by weight of the diethanolamine salt of (2-carb0Xybutyl)propylphosphonic acid.

11. A static electricity resistant cotton fiber comprising cotton havingdeposited upon the surface thereof, from about 0.5% toabout 3% by weightof the diethanolamine salt of (Z-carboxyoctyl) propylphosphonic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,304,157 12/1942 Engelmann et al. 260500 2,963,45 8 12/1960 Swern 26030.6 2,971,0192/1961 Ladd et al 260946 FOREIGN PATENTS 1,03 8,692 9/ 1958 Germany.

OTHER REFERENCES Nylen Berichte der Deutsche Chemischen Gersellschaft,59, pp. 1119-1128 (1926).

MURRAY KATZ, Primary Examiner.

T. G. DAVIS, Assistant Examiner.

1. A STATIC ELECTRICITY RESISTANT FIBER COMPRISING A FIBER SELECTED FROMTHE GROUP CONSISTING OF COTTON, CELLULOSE ACETATE, POLYETHYLENETEREPHTHALATE, AND ACRYLONITRILE POLYMER HAVING DEPOSITED UPON THESURFACE THEREOF FROM ABOUT 0.5% TO ABOUT 3% BY WEIGHT OF A COMPOUNDSELECTED FROM THE GROUP CONSISTING OF (A) A COMPOUND OF THE FORMULA: